Quaternary ammonium metal compounds



United States Patent 3,294,827 QUATERNARY AMMONIUM METAL COMPOUNDS Ronald R. Swanson, Minneapolis, Minn., assignor to General Mills, Inc., a corporation of Delaware No Drawing. Filed Sept. 26, 1961, Ser. No. 140,691 12 Claims. (Cl. 260429) This invention relates to novel quaternary ammonium compounds.

It is an object of this invention to provide novel quaternary ammonium metal compounds. It is another object of this invention to provide the novel process for the preparation of quaternary ammonium metal compounds. Other objects will appear hereinafter.

The objects of this invention are accomplished by a fatty quaternary ammonium metal compound wherein the anion of said quaternary compound is an inorganic anion containing a metal of Group VIIB of the Periodic Table. The compounds of the present invention are represented by the following formula:

where X is a fatty quaternary ammonium cation and Y is an inorganic anion containing .a metal of Group VIIB of the Periodic Table, and m is the valence of the inorganic anion.

As used herein, the term fatty refers to an aliphatic hydrocarbon radical of 8-24 carbon atoms. The term fatty quaternary ammonium refers to a quaternary ammonium compound having at least 1 fatty radical attached to the quaternary nitrogen atom. As used herein, the term metals of Group VIIB of the Periodic Table refers to manganese, technetium (masurium) and rhenium, as shown in the Periodic Table set forth on page 573 of General Inorganic Chemistry by Sneed and Maynard, Van Nostrand, New York, 1942.

The compounds of the present invention are prepared by reacting fatty quaternary ammonium compounds, particularly the fatty quaternary ammonium chlorides, with a salt having the desired metal containing anion. Using this procedure, the fatty quaternary ammonium compound is dissolved in an organic solvent and contacted with aqueous solution of an inorganic salt having the metal containing inorganic anion.. The aqueous solution is then discarded and the organic solvent removed from the organic phase by distillation, preferably under vacuum, to yield the product of the present invention.

Because of the availability of quaternary ammonium chlorides, they are generally used as a starting material in the preparation. However, other quaternary ammonium salts can be used with equal success. Suitable quaternary ammonium compounds for the preparation of the compounds for the present invention include trimethyl octyl ammonium chloride, methyl triisooctyl ammonium chloride, dimethyl dioleyl ammonium chloride, monomethyl trioleyl ammonium chloride, tetrapalmityl ammonium chloride, trimethyl myristyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl tallow ammonium chloride, dimethyl dicoco ammonium chloride, wherein coco refers to fatty radicals derived from coconut oil fatty acids, methyl octyl morpholium chloride, dilauryl morpholium chloride, lauryl stearyl morpholium chloride, octyl pyridinium chloride, stearyl pyridinium chloride, methyl trilinoleyl ammonium chloride, trioctyl benzyl ammonium chloride, stearyl tribenzyl ammonium chloride, and butyl lauryl dibenzyl ammonium chloride. The quaternary ammonium compound can be saturated, or contain ethylenic, acetylenic, or aromatic unsaturation. Generally, the quaternary ammonium compound may contain other functional groups, although it is generally preferred to employ compounds containing functional groups 3,294,827 Patented Dec. 27, 1966 which will remain inert during the preparative procedure. The term caprylyl used herein refers to the hydrocarbon radicals (octyl and decyl) derived from amixture of caprylic acid and capric acid.

Another method for preparing the compounds of the present invention is by contacting the quaternary ammonium starting material with a simple metallic salt. The quaternary and the metal salt are combined in a mutual solvent and, upon removing the solvent, the desired quaternary ammonium metal compound is prepared. For example, if it is desired to prepare a quaternary ammonium compound having an anion MnClf, this can be done by contacting quaternary ammonium starting material with manganese chloride in a mutual solvent such as other or isopropanol. While the product must be completely soluble in the chosen solvent, it is not generally necessary that both the starting quaternary compound and the metallic salt be completely soluble in the solvent, but it is only necessary that they be partially soluble. This technique is most useful when the anion of the quaternary ammonium compound is identical to the anion of the metal compound. For example, the quaternary ammonium chloride should be used to prepare the manganese chloride complex from the manganese salt. One advantage of this technique and a highly unusual feature of the present invention is that it is possible to prepare, by this method, anions which could not otherwise be prepared because of their instability in water.

Using the above described preparative procedures, fatty quaternary ammonium compounds having the following anions can be prepared: MnO MnO Mn OF f z s' 'I 15 z zf l3 2'7 Mn O MnCl MnF Mn(CN) Mn(CN) 6 f 3 2 4) 2 2 21 MHO2 2, Ml'lF5 ReOf ReO3 ReCl Rock R62O8 2, ReF ReI5 ReSO ReS2O2 ReS O ReBr6 ReI Re2OCl1o ReCl OH* TCO4 1. other compounds containing other anions containing metals of Group VIIB will be obvious to those skilled in the art.

In order to illustrate certain preferred embodiments of the present invention, the following examples are included. Unless otherwise indicated, all parts and percentages used herein are by weight.

Example 1 where R is caprylyl. The product analyzed 4.85% manganese, 13.3% chlorine and 2.65% nitrogen as compared theoretical values of 4.92%, 12.7%, and 2.51%, respectively.

Example II To 500 ml. of methanol were added 37.7 g. of MnSO 24.5 g. of NaCN and 486 g. of methyl tricaprylyl ammonium cyanide. After filtering, the solvent was evaporated under vacuum. The residue was dissolved in benzene, filtered and stripped of solvent under vacuum. There was obtained a dark viscous liquid product having the structural formula (R NCH Mn(CN) Example III I To 2.73 g. of NaReO in ether were added 5.86 g. of dimethyl distearyl ammonium chloride. After filtering 3 the solvent was evaporated to yield light yellow solid product of the formula R N(CH ReO where R is stearyl.

Example IV To 172.5 g. of NaMnO -H O in 500 ml. of methanol were added 420 g. of trimethyl caprylyl ammonium chloride. After filtering and evaporating the solvent, the residue was recrystallized from dimethyl formamide. There was obtained a dark brownish green solid product of the formula (RN(CH MnO where R is caprylyl.

The foregoing examples are illustrations of certain preferred embodiments of the present invention and are not to be construed as limitations on the scope thereof. The compounds of the present invention are useful as sizing materials for papers, cellulosic materials, polyamides, glass, vitreous and ceramic compositions, as fungicides, as pesticides, as biocides, as bactericides, as anti-barnacle coatings, as corrosion inhibitors, as dyes, as pigments, as colorants, as ultraviolet protectors, as wood preservatives, as additives for plastic materials, as additives for adhesives, as additives for glass laminates, as an additive for printing inks for plastics, as fuel and gasoline additives, as lubricant additives, as coating additives, as materials of construction for nuclear engineering, as accelerators for curing of synthetic resins, as catalysts for emulsion polymerization, as catalysts for intermediate materials for the preparation of catalysts for a variety of chemical reactions, as additives for vinyl plastisols, as electroplating materials, as a source of pure metals having unusual properties because of their complex nature, as vapor-phase plating chemicals, as anti-static additives for plastics and coatings, and the like. The products of the present invention can also be used to impregnate ceramics, silica, clay, alumina, and the like, and after firing the impregnated material, a product is obtained having the desired metal uniformly impregnated throughout the material.

The embodiments of the present invention in which an exclusive property or privilege is claimed, are defined as follows:

1. Complex compounds of the structure where X is a fatty quaternary ammonium cation wherein at least one of the four organic groups attached to the nitrogen atom is an aliphatic hydrocarbon radical of 824 carbon atoms, Y is an inorganic anion containing a metal of Group VIIB of the Periodic Table of Elements and m is the valence of said anion.

2. The complex compounds of claim 1 wherein the metal is manganese.

3. The complex compounds of claim 1 wherein the metal is technetium.

4. The complex compounds of claim 1 wherein the metal is rhenium.

5. Complex compounds of the formula:

where X is a fatty quaternary ammonium cation wherein at least one of the four organic groups attached to the nitrogen atom is an aliphatic hydrocarbon radical of 8-24 carbon atoms.

6. Complex compounds of the formula:

where R is selected from the group consisting of octyl and decyl.

7. Complex compounds of the formula:

where X is a fatty quaternary ammonium cation wherein at least one of the four organic groups attached to the nitrogen atom is an aliphatic hydrocarbon group of 8-24 carbon atoms.

8. Complex compounds of the formula:

where R is selected from the group consisting of octyl and decyl.

9. Complex compounds of the formula:

where X is a fatty quaternary ammonium cation wherein at least one of the four organic groups attached to the nitrogen atom is an aliphatic hydrocarbon group of 8-24- carbon atoms.

10. The complex compound of the formula:

RZN 2RO4 where R is stearyl.

11. Complex compounds of the formula:

where R is selected from the group consisting of octyl and decyl.

References Cited by the Examiner UNITED STATES PATENTS 2,580,473 1/1952 Sowa et a1. 260--429 2,798,103 7/1957 Schaffer et al. 260429 2,902,401 9/1959 Harwood et al 260429 OTHER REFERENCES Karrer: Organic Chemistry, 2nd English edition, Elsevier Publishing Co., New York, N.Y., 1946, page 119.

HELEN M. MCCARTHY, Acting Primary Examiner.

ABRAHAM H. WINKELSTEIN, TOBIAS E. LEVOW,

Examiners.

W. I. VAN BALEN, T. L. IAPALUCCI, Assistant Examiners. 

1. COMPLEX COMPOUNDS OF THE STRUCTURE 